Fluosilicates of organic aliphatic bases



Patented July 11, 1933 UNITED STATES 1,917,463 PATENT? OFFICE PAUL LAWRENCE SALZBERG AND EUCLID Will-FRED BOUSQUET, F WILHINGTONQDELA- WARE, ASSIGNOBB TO B. L DU PONT DE NEMOUBS dc COMPANY, 01' WILMINGTON, ZOE-AWARE, A OOBPORA'I'ION O1! DELAWARE FLUOBILIOATR OF OBGANIO ALIPHATIG BASES 11o Drawing.

This invention relates to new com ounds consisting of organic fluosilicates, an more articularly to the fluosilicates of aliphatic uses.

It is known that some of the organic aromatic bases react with hydrofluosilicic acid to give well defined crystalline salts of the general formula R,.H SiF,, where R uals the organic residue containing one asic nitrogen atom. Jacobson and Pray have described the preparation and some properties of the fluosilicates of aniline, mono-methyl aniline and 0-, m-, and p-toluidine (J. A. C. S. 50, 3055 (1928)); Elber & Schott re orted similarl on the fluosilicates of hy roxylamine J. r. Ch. (82), 78,338 (1908)) and hydrazine J. pr. h. (2) 81,552 (1910)).

The production of fluosilicates of aliphatic bases, and the mode herein disclosed of preparing these fluosilicates is, however, believed to be new.

This invention has as an object the roduction of new compounds consisting of no silicates of aliphatic bases. A further object is the production of fluosilicates of this class which are water soluble. A still further object resides in the method of preparing the above. referred to fluosilicates of organic aliphatic bases.

These objects are accomplished by the following invention in which organic aliphatic bases are reacted in the presence of water with hydrofiuosilicic acid, and the fluosilicate appropriately separated from its aqueous solution in the reaction mixture.

With respect to the general method of preparing these fluosilicates of organic ali hatic bases we prefer to react, below 60 6., the

approximately aqueous hydrofluosilicic acid of commerce and the aliphatic base in equivalent or neutralizing amounts. Thus, if the aliphatic base is a mono-amine, two moles will be reached with one mole of hydrofluosilicic acid, and if the aliphatic base is a diamine, one mole will be reacted with one mole of the acid. Evaporation of the mixture at room temperature, preferably over sulfuric acid in a vacuum desiccator, ields the purewhite crystalline organic uosilicate. In some cases, it becomes practical to precipitate most of the organic fluosilicate from the aqueous reaction mixture by the slow addition of ethyl alcohol or acetone.

The following specific examples are illus- Appllcatlon filed October 16, 1880. Serial No. 489,280.

trative of the method of preparing our new compounds.

Exam 1 Two-tenths mole (14.6 g.) of n-butylamine was slowl poured into 0.1 mole (46.9 g.) of 30.7% by rofluosilicic acid while keeping the temperature below. C. Evaporation of the aqueous reaction mixture at room temperature over sulfuric acid in a vacuum desiccator gave a pure white 0 stalline product which was further purified v washing'with several portions of ether. The whiteproduct when dry weighed 25 grams. This compound is quite volatile and sublimes ve readily. It is very soluble in water, insolub e in ether and benzene and only'slightly soluble in only slightly soluble in acetone and ethyl alcohol. 7

Q Exam 8 An aqeuous solution of 0.05 mole (28.45 g.) of 30.7% h drofluosilicic acid was treated with 0.1 mo c (18.5. of tri-n-butylamine with the temperature ow 60 G. Evaporation of this mixture gave a white crystalline product which was ve soluble in water but nsoluble in ether and no. The resultmg compound is quite hygroscopic. Exam 4 Benaylamim A fine white crystalline precipitate was ob tamed upon'addition of 0.2 mole (21.4.- of benzy amine'to 0.1 mole 46.9 g.) of 30.?96 hydrofluosilicic acid while eeping the temperature below 55 C. The mixture was concentrated by evaporation and diluted with absolute eth 1 alcohol. The resultin crystalline rodli ct, after washing with absolute ethyl alhohol and with ether, weighed 84,1 grams and did not melt below 235 C: This compound sublimes v readily. It is soluble in water and insolu le m ether and benzene.

One-tenth mole 14.9 g of triethanolamine was mixed with 0.05 mole (23.45 g.) of 30.7% hydrofluosilieic acid below 60f 0. Long white crystalline needles were obtained upon evaporation of the reaction m xture m a vacuum desiccator over phosphoric anhydride. This compound is very hygroscopic and absorbs moisture from the air very readily. It is soluble in alcohol, very soluble 1n water,and insoluble in ether and benzene.

'Exnmm 6 B-aminaetkyZ-anfliaw fluosilwat' e A solution of cc. of absolute ethyl alcohol and 0.1 mole (13.6 g.) of b-amino-ethylaniline was tl heated with 0.05 mole {23.45 'g.) o% d0.;% hydrofluosilicic ac1d.

he white crystalline preci itate was filtered, washed with ether and ied. This compound is insoluble in ether and benzene, only sli htly soluble in alcohol and ethyl acetate, and fairly soluble in water.

diamine to 0.2 mole 9 f 30.7% hydrofluosilicic acid. com and is moderately soluble in water, inso able in ether and benzene, and only very slightly soluble in ethyl alcohol and acetone.

The fluosilicates of organic aliphatic bases are in general white crystalline solids readil' g Soluble in water. They melt at fairly big temperatures, although rather volatile around 100 0., and some of them sublime. Analyses of these organic fluosilicates show that the possess the general formula R,H S' where R represents the organic aliphatic base containing one basic nitro atom. While it is to be understood that the present invention is not dependent or limited y the accuracy of the formulae used to represent our new compounds, it may be noted that where the aliphatic base contains a plurality of basic nitrogen atoms in the molecule, as for instance the ethylene diamine mentioned, the formula may be more generally expressed as wherein R is an aliphatic basic nitrogen cules having other functional compound, and :v the number of basic nitrogen atoms utilized for the formation of the uosilicate. When the base contains a plurality of nitrogen atoms in the molecule several possibilities exist. For instance, if two nitrogen atoms are present in each molecule of the aliphatic base, the H,SiF, group may be connected to one nitrogen atom of one molecule of the base and to one nitrogen atom of another molecule of the base, or both nitrogen atoms of one molecule of the base may be connected to the hydrofiuosilicic acid group, or two molecules of the acid group may connect two molecules of the base, one molecule of the acid connecting a nitrogen atom of one molecule of the base with a nitrogen atom of the other molecule of the base, and the other acid molecule like wise connecting the two remaining nitrogen atoms.

Our invention comprehends all or is aliphatic bases with a sufliciently basic nitrogen atom to react with hydrofluosilicic acid.

has the fluosilicates of alicyclic amines, such as cyclopentylamin'e or c clohexylamine, are included as well as the a 1, alkylene, and aralkyl amines. B the term aliphatic bases, we mean to in ude also molegroups besides the basic nitrogen atom, such as amino nitriles, mono-b-hydroxy ethyl amine, and amino acids. It is to be understood, therefore, that the term aliphatic as used in the claims to desi ate our new compounds consisting of the uosilicates of organic aliphatic bases, refers to the fact that at least one of the groups attached to the basic nitrogen atom, or atoms, is an aliphatic organic group, and that the term aliphatic includes those or '0 groups which are only partially alip atic,

ut which are joined to the nitrogen atom through the ali hatic constituent of the ormilgroup. us in the general formula fi ,Sil wherein R is an amino compound or group having a single basic nitrogen atom, this group may be represented as in which one of the R values is an aliphatic organic residue which, as noted above, may consist of an alkyl group an alkylene grou an aralkyl oup, or an alicycl'ic group. Tl fe remaining constituents may represent hydrogen or any one of the aliphatic groups referred to in connection with the mentioned value of R. a

While it is preferred to carry out the reaction betweenthe aliphatic base and hydrofluosilicic acid at a temperature below 60 C., or more specifically about room temperature, a wider range of temperature may be used, the highest tem erature being limlted by the boiling point 0 the aqueous mixture, or by the temperature that the organic fluosilicate decomposes. It is convenient to use commercial hydrofluosilicic acid which is about strength, but as long as the acid solution is not too dilute, other concentrations up to 100% may be used. An aqueous solution of these basic nitrogen compounds, soluble in water, may be reacted with hydrofluosilicic acid. The water present in the commercial acid is, however, sufiicient to carry out the reaction.

These compounds and compositions containing them are useful as wool-preservatives, disinfectants, and antiseptics.

The organic fluosilicates of the present invention are easily prepared white, crystalline, non-inflammable solids, soluble in water, practically odorless and non-corrosive.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

b 1. A fluosilicate of an organic aliphatic ase.

2. A water soluble fluosilicate of an organic aliphatic base.

3. A fluosilicate having the probable general formula of wherein R is an aliphatic basic nitrogen compound, and a: the number of basic nitrogen atoms in each molecule of the basic nitrogen compound which are utilized for the formation of the fluosilicate.

4. A fluosilicate having the probable general formula of a B B:

wherein R signifies a basic nitrogen compound of the structure of RI RI|-R' in which one of the R values represents an organic ali hatic radical, each of the remaining R values representing a univalent constituent selected from the class consisting of hydrogen and an organic aliphatic radical.

5. A process which comprises reacting hygrofluosilicic acid with an organic aliphatic ase.

6. A rocess which comprises reacting together ydrofluosilicic acid and an organic aliphatic base in the presence of water, and separating the organic aliphatic fluosilicate formed from the ueous reaction mixture.

7. A recess whic comprises reacting together ydrofluosilicic acid and an organic aliphatic base in the presence of water, below 0., and separatin the organic aliphatic fiuosilicate formed roin the aqueous reaction mixture.

In testimony whereof we afiix our signatures.

PAUL LAWRENCE SALZBERG. EUCLID WILFRED BOUSQUET.

CERTIFICATE OF CORRECTION Patent No. 1,917,463.

July 11, 1953 PAUL LAWRENCE SALZBERG. ET AL.

It is hereby certified that error appears in the printed specification or the above numbered patent requiring correction as follows:

Page 3,

line 12,

for "wool-preservatives" read wood-preservatives; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 19th day of May, A. D. 1956.

(Seal) decomposes. It is convenient to use commercial hydrofluosilicic acid which is about strength, but as long as the acid solution is not too dilute, other concentrations up to 100% may be used. An aqueous solution of these basic nitrogen compounds, soluble in water, may be reacted with hydrofluosilicic acid. The water present in the commercial acid is, however, sufiicient to carry out the reaction.

These compounds and compositions containing them are useful as wool-preservatives, disinfectants, and antiseptics.

The organic fluosilicates of the present invention are easily prepared white, crystalline, non-inflammable solids, soluble in water, practically odorless and non-corrosive.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

b 1. A fluosilicate of an organic aliphatic ase.

2. A water soluble fluosilicate of an organic aliphatic base.

3. A fluosilicate having the probable general formula of wherein R is an aliphatic basic nitrogen compound, and a: the number of basic nitrogen atoms in each molecule of the basic nitrogen compound which are utilized for the formation of the fluosilicate.

4. A fluosilicate having the probable general formula of a B B:

wherein R signifies a basic nitrogen compound of the structure of RI RI|-R' in which one of the R values represents an organic ali hatic radical, each of the remaining R values representing a univalent constituent selected from the class consisting of hydrogen and an organic aliphatic radical.

5. A process which comprises reacting hygrofluosilicic acid with an organic aliphatic ase.

6. A rocess which comprises reacting together ydrofluosilicic acid and an organic aliphatic base in the presence of water, and separating the organic aliphatic fluosilicate formed from the ueous reaction mixture.

7. A recess whic comprises reacting together ydrofluosilicic acid and an organic aliphatic base in the presence of water, below 0., and separatin the organic aliphatic fiuosilicate formed roin the aqueous reaction mixture.

In testimony whereof we afiix our signatures.

PAUL LAWRENCE SALZBERG. EUCLID WILFRED BOUSQUET.

CERTIFICATE OF CORRECTION Patent No. 1,917,463.

July 11, 1953 PAUL LAWRENCE SALZBERG. ET AL.

It is hereby certified that error appears in the printed specification or the above numbered patent requiring correction as follows:

Page 3,

line 12,

for "wool-preservatives" read wood-preservatives; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 19th day of May, A. D. 1956.

(Seal) 

